JP2547324C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   [Industrial applications]   The present invention relates to a method for forming an image using a positive photoresist, and a method useful for the method.
The present invention relates to a photosensitive composition and a support for supporting an image formed by the method.
Things.   [Problems to be solved by conventional technology and invention]   In forming an image using a positive photoresist, the part exposed to actinic radiation
The photoresist becomes more soluble or less soluble in the developer than unexposed areas.
If not, it can be more easily removed by the developer. Unexposed parts
By leaving it as it is and removing the desired exposed portion with a developer, the image of the
It is formed.   Commercially available positive photoresist compositions are usually in addition to film-forming organic materials,
Exposure to actinic radiation decomposes and releases nitrogen, forming indene carboxylic acid
O-naphthoquinonediazide. Film-forming organic materials are usually
It is a lukali soluble phenol formaldehyde novolak resin. Its alkali
Dissolution in aqueous solution is inhibited by naphthoquinonediazide:
When the diazide in the irradiated part is decomposed, its effectiveness as a solubility inhibitor decreases,
The solubility of the exposed part of the coating in the basic developer is greater than that of the unexposed part.
It will be good. However, quinonediaside is unstable to heat,
Decomposes at moderately elevated temperatures even in protected areas, resulting in poor quality images.
It's not completely satisfactory. In addition, these diazides dissolve
Must be used in relatively large proportions to be effective as a dissolution inhibitor
. Since these diazides absorb strongly at the preferred wavelengths of the ultraviolet, they contain
Composition is relatively hard to transmit ultraviolet radiation, and the radiation is deep in the coating.
Since it cannot penetrate, deep parts, for example, boundaries with the substrate, cannot be developed.   EP-A-0 166 682 describes a film-forming material.
Alpha or base on the carbon atom supporting the sulfonate ester group A sulfonate ester of an aromatic alcohol having a carbonyl group at the ta position, or
Using a composition comprising an N-sulfonyloxy derivative of an amide or imide
The formation of a positive image is described. Said European patent EP-A-0 666
82, but has higher sensitivity,
Therefore, there is a demand for an image forming method and a composition which promote a more rapid image formation.   When mixed with film-forming materials that are soluble in aqueous basic solvents, aromatic oximes
Rufonate reduces the rate of dissolution of the film-forming material in the solvent, but this effect
Fruits can now be neutralized by exposing the mixture to actinic radiation.
It became clear. Further, when a composition comprising the mixture is imaged by actinic radiation,
The solubility of the composition in aqueous basic developers increases rapidly in exposed areas
It was found that a good image was obtained after development.   [Means for solving the problem]   Therefore, one of the objects of the present invention is (I) supported on a substrate (A) a film-forming organic material; (B) Formula I: > C = NO-SO_Two− I At least one oxime sulfonate group and at least one aromatic group
A layer of a composition comprising a mixture with a photosensitive material having one is also predetermined.
Exposed to actinic radiation in an exposed pattern, thereby exposing the exposed portion of the composition.
More soluble in the basic developer than the uncoated part of the composition, and (Ii) removing the exposed portion of the composition by treating it with an aqueous basic developer;
And providing an image forming method.   Another object of the present invention is that it is suitable for performing the method of the present invention, (A) a film-forming organic material; (B) Formula I: > C = NO-SO_Two− I At least one oxime sulfonate group and at least one aromatic group
Used as a positive photoresist, consisting of a mixture with a photosensitive material having one It is to provide a composition to be used.   In the photosensitive substance (B), the carbon atom and the sulfur atom indicated in the formula I are usually
Although each is attached to a carbon atom, the sulfur atom may be attached to a nitrogen atom. Charcoal
Either a hydrogen atom or a sulfur atom must be bonded to a group containing an aromatic ring.
May be carbocyclic or heterocyclic aromatic rings. Preferably, the carbon source
The atom and the sulfur atom are each bonded to the group containing an aromatic ring. Substance (B) has the general formula
It has one or two groups represented by I.   Suitable oxime sulfonates (B) having a group of the formula I are usually of the formula II
: (In the formula,   R¹Is a monovalent aliphatic, carbocyclic, heterocyclic or aromatic having up to 20 carbon atoms
Represents an aliphatic group or a cyano group,   R^TwoIs the group R¹Or an unsubstituted or substituted amino group;¹And R^TwoBut it
A carbon ring having up to 20 carbon atoms together with the carbon atom to which they are attached
Forming a formula or a heterocyclic group,   R^ThreeIs an n-valent aliphatic, carbocyclic, heterocyclic group having up to 40 carbon atoms or
Represents a substituted or substituted amino group,   Where R¹, R^TwoAnd R^ThreeAt least one is a carbocyclic aromatic or heterocyclic aromatic
Group group,   m is 0 or 1, and   n is 1 or 2. ].   In a preferred embodiment of Formula II,   R¹Is an alkyl group having 1 to 12 carbon atoms, a halo having 1 to 4 carbon atoms.
Alkyl group, alkenyl group having 2 to 6 carbon atoms, alkenyl group having 5 to 12 carbon atoms
Chloroalkyl group, unsubstituted or the following group: halogen atom, having 1 to 16 carbon atoms
An alkyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms
From alkylthio, phenyl, phenoxy, phenylthio or nitro groups
C6-C6 substituted by one or more of the selected substituents Represents 10 aryl groups, or R¹Is a furyl, thienyl, tetrahydrofuran
Rufuryl group, aralkyl group having 7 to 12 carbon atoms, 1 to 8 carbon atoms
An alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, a phenoxy group or
Represents a cyano group,   R^TwoIs the group R¹Or an alkanoyl group having 2 to 6 carbon atoms, a benzoyl group, a carbon atom
An alkoxycarbonyl group having 2 to 5 atoms, a phenoxycarbonyl group, -N (
R^Four) (R^Five) Group, morpholino group or pipericino group;¹And R^TwoBut
Together with the carbon atom to which they are attached, a 5- to 8-membered ring or a benzo group or
Forms a 5- to 8-membered ring bonded to the two,   R^FourIs a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a carbon atom
Represents an alkanoyl group or a benzoyl group having 2 to 6 children;   R^FiveIs a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group
Represents   R as an alkyl group¹, R^Two, R^FourAnd R^FiveIs a linear or branched alkyl group.
And depending on the number of carbon atoms indicated, for example a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n
-Pentyl group, isoamyl group, n-hexyl group, 2-ethylbutyl group, n-octyl group
It may be a tyl group, 2-ethylhexyl group, n-decyl group or n-dodecyl group
.   R as a haloalkyl group having 1 to 4 carbon atoms¹Or R^TwoIs, for example, chloro
Methyl group, trichloromethyl group, trifluoromethyl group or 2-bromopropyl
Group.   R as a cycloalkyl group¹And R^TwoIs, for example, a cyclopentyl group,
It may be a xyl, cyclooctyl or cyclododecyl group.   R as an unsubstituted or substituted aryl group¹And R^TwoIs, for example, a phenyl group,
Fluorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2
, 6-dichlorophenyl group, p-tolyl group, 2,4-dimethylphenyl group, 4-
Isopropylphenyl group, 4-tert-butylphenyl group, 4-dodecylphenyl group
, 4-methoxyphenyl group, 4-butoxyphenyl group, 4-phenoxyphenyl A 4-biphenylyl group, a 3-nitrophenyl group, a 1- or 2-naphthyl group,
5-chloro-1-naphthyl group, 6-bromo-2-naphthyl group, 4-nitro-1-
It may be a naphthyl group or a 6-methoxy-2-naphthyl group. Furyl group or Thie
R as a nil group¹Is preferably a 2-furyl group or a 2-thienyl group.   R as aralkyl group¹And R^TwoIs, for example, a benzyl group, 1- or 2-phenyl
Nylethyl group, 3-phenylpropyl group, 2-phenylisopropyl group, 2-phenyl
It may be a phenylhexyl group or a naphthylmethyl group.   R as an alkoxy group¹Or R^TwoIs preferably a methoxy group or an ethoxy group.
R as a cycloalkoxy group¹Or R^TwoIs preferably cyclohexyloxy
A group represented by R as an alkoxycarbonyl group^TwoIs preferably methoxycarbonyl
Or an ethoxycarbonyl group. R¹And R^TwoAre the atoms to which they are attached
When taken together to form a 5- or 8-membered ring, these may be carbocyclic or heterocyclic rings
For example, cyclopentane, cyclohexane, cycloheptane, pyran or piperi
It may be a gin ring. This ring may also be attached to a benzo group, for example
Is tetrahydronaphthalene, dihydroanthracene, indene, chroman, full
Oren, xanthene or thioxanthene ring systems. This ring is also carboni
And cyclohexanedienones, naphthalenones and the like.
And anthrone ring systems.   In a further preferred embodiment of Formula II,   n is 1;   R¹Is an alkyl group having 1 to 6 carbon atoms, a haloal having 1 to 4 carbon atoms
Killed group, unsubstituted or chlorine atom, alkyl group having 1 to 4 carbon atoms, number of carbon atoms
One substituent selected from the group consisting of 1-4 alkoxy groups or nitro groups, or
Represents a phenyl group substituted by two, or a 2-furyl group, 2-cenyl
A C 1 -C 4 alkoxy or cyano group;   R^TwoIs the group R¹Or a silalkylamino group or a morpholino group;¹When
R^TwoIs bonded to one or two benzo groups together with the atoms to which they are attached
Represents a 5- or 6-membered ring which may be substituted.   In a particularly preferred embodiment of Formula II,   n is 1;   R¹Is an alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, phenyl
A chlorophenyl group, a dichlorophenyl group or a methoxyphenyl group,   R^TwoIs the group R¹Or a cyano group;¹And R^TwoAt least one is a phenyl group or
Represents a substituted phenyl group;¹And R^TwoIs the carbon atom to which they are attached
Together, indane, fluorene, tetrahydronaphthalene, anthrone or
Represents a dihydroanthracene ring system.   In formula II, R^ThreeIs an alkyl group, an alkylene group, a cycloalkyl group,
Loalkylene, aryl, arylene, aralkyl, or alkylalkyl
Represents any one of -O-, -S- and -NR.^Five-By group
May be interrupted, and any of these may be unsubstituted or halogen,
Kill group, haloalkyl group, aminoalkyl group, alkoxy group, aryloxy group
, Acyl group, acyloxy group, alkyl group, alkyloxy group, hydroxy
Group, carboxyl group, alkoxycarbonyl group, alkyl-CONH- group,
Enyl-CONH- group, H_TwoN-group, alkyl-NH-group, dialkyl-N-group
Or may be substituted by a nitro group;^ThreeIs an unsubstituted or substituted amino group
And R^FiveIs a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or
Represents a clohexyl group.   Therefore, suitable compounds of formula II are   n is 1 and R^ThreeIs an alkyl group having 1 to 18 carbon atoms;
Is a halogen atom, an alkyl group having 1 to 16 carbon atoms, and 1 to 4 carbon atoms.
A haloalkyl group, an aminoalkyl group having 1 to 4 carbon atoms,
An alkoxy group having 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, a carbon atom
Alkylcarbonyloxy, benzoyl, benzoyloxy having 1 to 4 carbon atoms
Si, hydroxyl, carboxyl, C1 -C4 alkoxy
A rubonyl group, an alkyl-CONH- group having 1 to 4 carbon atoms, phenyl-CO
NH- group, N_TwoAn N-group, an alkyl-NH- group having 1 to 4 carbon atoms, a di (carbon
A carbon atom substituted by an alkyl having 1 to 4 atoms) -N- or a nitro group
Represents an aryl group having 6 to 10 children;^ThreeIs 5 to 12 carbon atoms A cycloalkyl group; an aralkyl group having 7 to 9 carbon atoms;
A tyl group; or a trichloromethyl group; or   n is 2 and R^ThreeIs an alkylene group having 2 to 12 carbon atoms,
C 6 -C 15 arylene group or C 7 -C 12 aralkylene
Any of which is unsubstituted or has 1 to 16 carbon atoms.
Substituted by an alkyl group, a halogen atom, or a hydroxyl group;
Any of which is -O-, -S-, or -NR^Five-Groups (wherein, R^FiveIs a hydrogen atom
, An alkyl group having 1 to 12 carbon atoms or a cyclohexyl group. By)
Is a compound that may be interrupted.   Alkyl group, haloalkyl group, alkoxy group, cycloalkyl group or aralkyl
R as a kill group^ThreeIs R¹And R^TwoAny of the groups described for
Good. R as a substituted and / or interrupted alkyl group^ThreeIs one of the following groups
May be: -CH_TwoCH_TwoOH group, -CH_TwoCH_TwoNH_TwoGroup, -CH_TwoCH (O
H) CH_TwoOH group, -CH_TwoCH_TwoOCH_ThreeGroup, -CH_TwoCH_TwoOCH_TwoCH_TwoOH group, -CH_TwoCH_TwoSCH_TwoCH_TwoOH group or -CH
_TwoCH_TwoNHCH_TwoCH_TwoNH_TwoBase.   R as an unsubstituted or substituted aryl group^ThreeIs an unsubstituted or substituted aryl group,
Chloromethylphenyl group, 4-bromomethylphenyl group, 4-aminomethylphen
Nyl, 4-acetylphenyl, 4-acetyloxyphenyl, 4-hydro
Xyphenyl group, 2,5-dihydroxynaphthyl group, 4-carboxyphenyl group
, 3-carboxyphenyl group, 3,4-dicarboxyphenyl group, 4-carboxy
Cimethoxyphenyl group, 4-methoxycarbonylphenyl group, 3-ethoxycal
Bonylphenyl group, 4-methylcarbonylphenyl group, 4-aminophenyl group,
R such as 4-methylaminophenyl or 4-dimethylaminophenyl¹When
R^TwoMay be any of the groups mentioned for   R as an optionally interrupted and substituted alkylene group^ThreeIs linear or branched
Chain alkylene groups such as ethylene, 1,2-propylene, 1,3-propylene
Group, tetramethylene group, hexamethylene group, octamethylene group, -CH_TwoCH_TwoOCH_TwoCH_Two-Group, -CH_TwoCH_TwoOCH_TwoCH (OH) CH_Two-Group, -CH_TwoCH_TwoSCH_TwoCH_Two-Group or -CH_TwoCH_TwoNHCH_TwoCH_Two-May be a group.   R as an optionally substituted arylene group^ThreeIs a 1,3-phenylene group,
1,4-phenylene group, 2-methyl-1,3-phenylene group, 5-chloro-1,
2-phenylene group, 6-hydroxy-1,3-phenylene group, 4,4′-dife
Nylene group, oxy-4,4'-diphenylene group, oxy-4,4'-dihydroxy
C-3,3'-diphenylene group, 1,4-naphthylene group, 2,7-naphthylene group
, 1,3-naphthylene group, 7-chloro-1,4-naphthylene group, 5,8-dihydrido
Roxy-1,4-naphthylene group, methylenebisphenylene group, or isopropyl
It may be a denbisphenylene group.   R as an optionally substituted aralkylene group^ThreeIs -p-CH_Two-Ar-
Group, -p-CH_TwoCH_TwoOCH_Two-Ar- group, -p-CH_TwoCH_TwoO-Ar- group,-
p-CH_Two-Ar-CH_Two-Group or -p-CH_TwoCH (OH) CH_TwoO-Ar- group (
In the above formulas, Ar represents a benzene ring).   Preferably, n in Formula II is 1 and R^ThreeIs an atom having 1 to 12 carbon atoms.
Alkyl group, or unsubstituted or halogen atom, alkyl group having 1 to 16 carbon atoms
Or a hydroxyl group, particularly preferably a 4-chlorophenyl group, a 4-tolyl group and
Represents a phenyl group substituted by a 4-dodecylphenyl group.   Particularly preferred compounds of the formula II are   R¹And R^TwoOne of them represents a phenyl group or a 4-methoxyphenyl group, and
And the other represents a cyano group or¹And R^TwoIs the carbon atom to which they are attached
Together form a fluorene or anthrone ring system,   R^ThreeRepresents a 4-tolyl group, a 4-chlorophenyl group or a 4-dodecylphenyl group.
eagle, I,   m is 0, and   A compound in which n is 1.   Wherein m = 0 and n = 1, examples of particularly preferred compounds of the formula II
Α- (4-toluenesulfonyloxyimino) benzyl cyanide (R¹ = Phenyl group, R^Two= -CN group, R^Three= 4-tolyl group), α- (4-chlorobenze)
Sulfonyloxyimino) benzyl cyanide (R¹= Phenyl group, R^Two= -C
N group, R^Three= 4-chlorophenyl group), α- (4-dodecylbenzenesulfonyl)
Oxyimino) benzyl cyanide (R¹= Phenyl group, R^Two= -CN group, R^Three=
4-dodecylphenyl group), α-[(4-toluenesulfonyloxyimino)-
4-methoxyphenyl] acetonitrile (R¹= 4-methoxyphenyl group, R^Two=
-CN group, R^Three= 4-tolyl group), 9- (4-dodecylbenzenesulfonyloxy)
Shimino) fluorene (R¹And R^TwoTogether with the carbon atom to which they are attached
To form a fluorene ring system;^Three= 4-dedosylphenyl group), and α-
[(Dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] ace
Tonitrile (R¹= 4-methoxyphenyl group, R^Two= -CN group, R^Three= 4-dodeci
Ruphenyl group).   The compound of the formula II is preferably an oxime of the formula II1
: [In formulas III and IV, R¹, R^Two, R^Three, M and n are as defined above.
The same meaning).
Can be manufactured.   This reaction is usually performed in an inert organic solvent in the presence of a tertiary amine. Group R^ThreeIs official
Functional groups such as a carboxyl group, a hydroxyl group or an amino group,
Substituted sulfonic acids such as sulfanilic acid, phenolsulfonic acid and naphtho
The sulfonyl chloride of sulfonic acid can be used, or
It can also be introduced after the sulfonylation of the shim.   The oximes required for the reaction are prepared in customary manner, for example with the corresponding carbonyl compounds.
Reacting with hydroxylamine to give a nitration of the reactive methylene group, for example
Nitration of benzyl cyanide with, for example, methyl nitrite, or aromatic hydroxy
The compound can be obtained by nitrating a compound.   Preferred and other compounds of the formula II and their preparation are described in US Pat. U.S. Pat. Nos. 4,351,935 and 4,540,598.
(These include curing agents for aminoplast and phenolic resole resins)
The use of said compounds as is described).   The oxime sulfonate (B) is preferably 0.05 to 0.8, particularly preferably.
0.2 to 0.6 parts by weight based on parts by weight of the film-forming organic material
Is done. Okis selected for use with specific film-forming materials (A)
Simsulfonates should not have groups that react substantially with the functional groups in (A)
Absent.   The film-forming organic material soluble in the aqueous base is preferably a phenolic hydroxyl group or
Is a group containing a carboxyl group or a sulfonic acid group. Such materials are carbo
Xyl-terminated polyesters, for example, by the reaction of a dihydric alcohol with a dicarboxylic acid.
Polyester. The dihydric alcohol that may be used is ethylene.
Glycol, diethylene glycol, and higher polyoxyethylene glycos
Propane-1,2-diol, dipropylene glycol, and higher order
Polyoxypropylene glycol; propane-1,3-diol; butane-1,
4-diol and polyoxytetramethylene glycol; bentan-1,5-di
Oar, resorcitol, quinitol, bis (4-hydroxycyclohexyl)
Includes methane, and 2,2-bis (4-hydroxycyclohexyl) propane.
The divalent carboxylic acids which may be used are aliphatic acids such as succinic acid, glutaric acid, adipic acid
, Pimelic acid, suberic acid, azelaic acid, or sebacic acid, dimerized linolein
Acids, aromatic acids such as phthalic, isophthalic, and terephthalic acids, and cycloaliphatic
Acids, such as hexahydrophthalic acid.   Preferred film-forming materials are homopolymers of ethylenically unsaturated phenols and
And polymers that are copolymers. Examples of such polymers include vinyl
And 1-propenyl-substituted phenols such as p-vinylphenol and p- (1-
Homopolymers of (propenyl) phenol and these phenols and other polymerizable compounds
Ethylenically unsaturated materials such as styrene, acrylates and vinyl esters
And copolymers with one or more of the following.   Preferred film-forming materials are acetoarthyde or furfural, but Preferably an aldehyde, such as formaldehyde, and phenol itself,
Or a phenol substituted with two chlorine atoms, such as p-chlorophenol,
Or phenol substituted with one or two alkyl groups having 1 to 9 carbon atoms
O-, m- and p-cresol, xylenol, p-tert-butylphenol
Phenol, p-nonylphenol, p-phenylphenol, resorcinol
, Bis (4-hydroxyphenyl) methane, and 2,2-bis (4-hydroxy
Novolak resins derived from phenols such as phenyl) propane.   Other suitable film forming materials are ethylenically unsaturated carboxylic acids and carboxylic anhydrides
Product homopolymers and copolymers. Such polymers include acrylic acid,
Homopolymers of tacrylic acid and maleic anhydride and their monomers and other
Tilenic unsaturated materials such as ethylene, propylene, acrylic acid and methacrylic acid
Esters, aliphatic unsaturated compounds such as vinyl esters such as vinyl acetate, and
One or more aromatic vinyl compounds such as styrene and substituted styrene
And copolymers of   The formation of an image is caused by a photosensitizer in the composition, that is, an excited state by irradiation, and an unexcited state.
Containing an energy donating compound to the aromatic oxime sulfonate (B)
Can be promoted. Such photosensitizers include condensed aromatic hydrocarbons and
Substituted derivatives, aromatic carbonyl compounds, aromatic nitro compounds and cations
And basic dyes. Individual groups of suitable photosensitizers include anthracene,
Luoranthen, pyrene, anthrone, 2-methyl- or 2-chloro-thioki
Thioxanthones such as Sandton, and benzophenones, especially 4,4'-bis (di
Bis such as methylamino) benzophenone (Michler's ketone)
(Dialkylamino) benzophenone. Image formation is easier to recognize
Use a dye like Crystal Violet to make the composition
You may put in.   To carry out the method of the invention, the layer of the composition to be imaged is solvent-e.g.
2-ethoxyethanol, 2-ethoxyethyl acetate, ethyl methyl ketone
, N-methylpyrrolidone, dimethylformamide, dioxane or a mixture thereof
From solvents such as compounds by conventional methods such as dipping, spinning, spraying, or Apply to the support using a roller. Then the solvent is allowed to stand or
Evaporation by heating to a temperature at which the dry or thermosetting component cures. Branch
The carrier is usually copper, aluminum or other metal, silicon, silicon oxide
Or a film of nitride, polyester, polyamide or polyolefin
Synthetic resin or plastic, paper, or glass such as
To a thickness of about 1 to 250 μm.   Actinic radiation of the composition in a predetermined pattern is substantially opaque
Or through a transparent image bearing body consisting of
This is performed by a laser beam controlled by a computer. Usually 200-60
0 nm actinic radiation is used and suitable sources include carbon arcs, mercury lamps, and ultraviolet light.
Fluorescent lamps containing radiating phosphorus, argon and xenon glow lamps, tungsten
Ten lamps and floodlights for photography. Mercury lamps and metal harass
Id ramps are most suitable. Exposure time depends on the nature of the composition used, layer thickness, source
Depends on factors such as type of source and distance between source and layer, typically less than 10 seconds
However, suitable exposure times are readily determined by routine experience.   After irradiation for image formation, the layer of the composition is washed with a developer, and the exposed portions,
That is, the irradiated portion is removed except for the unexposed portion. The developer is exposed
Dissolve or remove easily by gentle brushing or stirring
I will do it.   The aqueous basic developer may be an aqueous solution of a strong base such as triethylamine.
An aqueous solution of lukali, such as sodium hydroxide, sodium carbonate or dihydrogen phosphate
Sodium is preferred. Small amounts, typically 5-15% by volume, to speed development
, A water-miscible lower aliphatic alcohol such as methanol.   After exposure and development, the remaining coating on the unexposed parts
To remove exposed metal and form a printed circuit, while protecting the printed circuit; or
The substrate can be etched to increase the depth of the image and increase the difference
You. Suitable etching methods, such as ferric chloride or ammonium persulfate on copper substrates
The use of a solution of nickel is well known. If desired, remove the remaining coating
Imaging the entire substrate to render it soluble in a basic solution and reveal the underlying substrate Exposure to actinic radiation can be for an extended period of time in a manner independent of.   In another post-development method, when the substrate is made of metal, it is, for example, copper, tin,
Irradiation without forming an image, for example, as a plate using a metal such as lead or nickel
Removes the unexposed polymerizable film and removes the exposed metal
Etching is performed by the same method as described above.   The method according to the invention is suitable for the production of printing plates and printed circuits, integrated circuits or hybrid circuits.
Useful.   The following examples illustrate the invention in more detail. Parts are by weight unless otherwise specified
Indicates a part.   α- (4-toluenesulfonyloxyimino) benzyl cyanide is as follows
Produced by the method:   α-hydroxyiminobenzyl cyanide (methanol and sodium methoxy
Reaction of benzyl cyanide with methyl nitrite in a mixture with
(14.6 g, 0.1 mol) was dissolved in tetrahydrofuran (50 g).
And then cool the solution to -8 ° C. Add triethylamine (15
. 2 g), followed by 4-toluenesulfone in tetrahydrofuran (50 g).
Nyl chloride (19.1 g, 0.1 mol) is added. The addition rate is 0 ° C at the reaction temperature.
Adjust to maintain: If the stirring is continued, the reaction temperature rises to room temperature (
About 2 hours). The mixture is poured into 11 of cold water containing concentrated hydrochloric acid (13 ml). White
A crystalline precipitate is obtained, which is recrystallized from ethanol. The product has a melting point of 133-1.
Has 34 ° C. Its infrared spectrum measured by KBr tablet is 1600
, 1390, 1300, 1190, 1180, 1160, 1090, 910, 8
30, 810, 770, 730, 680, 670 and 640 cm^-1To maximum absorption
Show. Proton NMR spectrum has multiple aromatic peaks at 7.5 to 8.2 ppm.
And a single peak at 2.4 ppm (-CH_Three).   Other oxime sulfonates used in the examples are suitable in a similar manner.
It is manufactured from oximes.   [Effects of Examples and the Invention] Example 1   Softening point in dimethylformamide (DMF) (2 parts) and dioxane (8 parts)
136 ° C mixed cresol novolak (4 parts) and α- (4-toluenesulfonate)
A solution of (roximino) benzyl cyanide (1 part) is prepared. Wash the mixture
And dried at 90 ° C. for 5 minutes to form a coating having a thickness of 7 μm. Suffered
Using a 5000 W metal halide lamp at a distance of 75 cm for the film, through the negative
Irradiate for 15 seconds. 30 seconds when developed with 1.5% aqueous sodium hydroxide
And an excellent image can be obtained. Example 2   Softening point in dimethylformamide (DMF) (2 parts) and dioxane (8 parts)
136 ° C mixed cresol novolak (4 parts) and α- (4-chlorobenzenes)
A solution of (ruphonyloxyimino) benzyl cyanide (1 part) is prepared. The mixture
Apply to the washed copper-clad laminate and dry at 90 ° C for 5 minutes to form a 6 µm thick coating.
You. Using a 5000 W metal halide lamp at a distance of 75 cm,
And irradiate for 30 seconds. When developed with 1.5% aqueous sodium hydroxide solution
An excellent image can be obtained in 30 seconds. Example 3   2-ethoxyethanol, 2-ethoxyethyl acetate in a volume ratio of 2: 2: 1
With a softening point of 136 ° C in a solvent mixture (8 parts) consisting of
Cresol novolak and α- (4-dodecylbenzenesulfonyloxyimino)
) A solution of benzyl cyanide (1 part) is prepared. Copper-clad laminate washed mixture
And dried at 90 ° C. for 5 minutes to form a film having a thickness of 5 μm. 75cm for coating
Using a 5000W metal halide lamp at a distance of 30 seconds through the negative
You. Excellent image was obtained in 30 seconds when developed using 2% aqueous sodium hydroxide solution.
It is. Example 4   Mixed cresol with a softening point of 136 ° C in DMF (2 parts) and dioxane (8 parts)
Novolak (4 parts) and α- (4-toluenesulfonyloxyimino) -4-me
A solution of toxic-phenylacetonitrile (1 part) is prepared. Washed the mixture
It is applied to a copper-clad laminate and dried at 90 ° C. for 5 minutes to form a film having a thickness of 5 μm. Coating Using a 5000 W metal halide lamp at a distance of 75 cm
Irradiate for 0 seconds. Excellent when developed with 2% aqueous sodium hydroxide solution in 45 seconds
Image is obtained. Example 5   2-ethoxyethanol, 2-ethoxyethylacete in a volume ratio of 2: 2: 1: 1
Softening point 1 in solvent mixture (8 parts) consisting of ethyl acetate, ethyl methyl ketone and DMF
36 ° C mixed cresol novolak and 9- (4-dodecylbenzenesulfonyl)
A solution of (oximino) fluorene (1 part) is prepared. Copper clad washed mixture
It is applied to a laminate and dried at 90 ° C. for 5 minutes to form a film having a thickness of 5 μm. 7 on the coating
Using a 5000 W metal halide lamp at a distance of 5 cm, through the negative for 30 seconds
Irradiate. Excellent image in 2 minutes when developed using 1.5% aqueous sodium hydroxide solution
An image is obtained. Example 6   Methyl methacrylate, 2-hydride in DMF (2 parts) and dioxane (8 parts)
Roxyethyl methacrylate and methacrylic acid (weight ratio 50:40:10, acid value
1.0 eq / kg) (4 parts) and α-[(
4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile
(1 part). Apply the mixture to the washed copper clad laminate,
Dry at 90 ° C. for 5 minutes to form a film having a thickness of 5 μm. 5 on the coating at a distance of 75 cm
Irradiate through a negative for 10 seconds using a 000 W metal halide lamp. 2% water
Excellent image can be obtained by developing for 20 seconds using an aqueous solution of sodium oxide followed by washing with water.
can get. Example 7   Tert-butylphenol-phenol in DMF (2 parts) and dioxane (8 parts)
Lunovolac (molar ratio 30:70, softening point 125 ° C) (4 parts) and α-[(4-
Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (
1 part). The mixture is applied to the washed copper-clad laminate and
Dry for 7 minutes to form a 7 μm thick film. 5000W at a distance of 75cm to the coating
Irradiate through a negative for 30 seconds using a metal halide lamp. 1% sodium hydroxide An excellent image can be obtained in 15 seconds by developing using an aqueous solution of chromium. Example 8   Having a weight average molecular weight of 10,000 in DMF (2 parts) and dioxane (8 parts)
From Maruzen Oil Co., Ltd., Tokyo, Japan as trade name "Resin M Grade S-4"
Commercially available poly (p-vinylphenol) (4 parts) and α- (4-toluene
A solution of sulfonyloxyimino) benzyl cyanide (1 part) is prepared. blend
Is applied to the washed copper-clad laminate and dried at 90 ° C. for 5 minutes to form a film having a thickness of 10 μm.
make. Using a 5000 W metal halide lamp at a distance of 75 cm,
For 30 seconds. Develop using 0.5% aqueous sodium hydroxide solution
And an excellent image can be obtained in 30 seconds. Example 9   2-ethoxyethanol, 2-ethoxyethyl acetate in a volume ratio of 2: 2: 1
With a softening point of 136 ° C in a solvent mixture (8 parts) consisting of
Cresol novolak (4 parts) and α-[(4-dodecylbenzenesulfonyl
Xyimino) -4-methoxyphenyl] acetonitrile (1 part)
You. The mixture was applied to the washed copper-clad laminate and dried at 90 ° C. for 5 minutes to a thickness of 10
Make a μm coating. 5000W metal halide lamp at a distance of 70cm on the coating
Irradiate through negative for 30 seconds. Develop in 2% aqueous sodium hydroxide solution
Then, an excellent image can be obtained in 20 seconds.

Claims (1)

And Claims (1) (i) is supported on the substrate (A) film-forming organic material, (B) the following formula I:> C = N-O -SO 2 - oxime represented by I Exposing a layer of a composition comprising a mixture with a photosensitive material having at least one of a sulfonate group and at least one of an aromatic group in a predetermined pattern to actinic radiation, whereby the composition of the exposed part An image-forming method comprising: rendering the exposed portion of the composition more soluble in the basic developer than the unexposed portion of the composition; and (ii) removing the exposed portion of the composition by treatment with an aqueous basic developer. (2) The indicated carbon atom or sulfur atom in the substance (B) is bonded to a group containing an aromatic ring, or the indicated carbon atom and the indicated sulfur atom each contain an aromatic ring. A method according to claim 1, wherein the method is coupled to (3) The substance (B) has the following formula II: Wherein R ¹ represents a monovalent aliphatic, carbocyclic, heterocyclic or araliphatic group having up to 20 carbon atoms, or a cyano group; R ² represents a group R ¹ or unsubstituted or substituted amino or it represents a group, or R ¹ and R ² together with the carbon atoms to which they are attached form a carbocyclic or heterocyclic group having up to 20 carbon atoms, R ³ is a carbon atom Represents an n-valent aliphatic, carbocyclic, heterocyclic group having up to 40 or an unsubstituted or substituted amino group, provided that at least one of R ¹ , R ² and R ³ is a carbocyclic aromatic or heterocyclic group; Containing a cyclic aromatic group, m is 0 or 1, and n is 1 or 2. The method according to claim 1, wherein the method is represented by the following formula: (4) In the formula II, R ¹ is an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms. , Unsubstituted or the following groups: halogen atom, 1 to 16 carbon atoms
With one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group, a phenylthio group and a nitro group. Represents an aryl group having 6 to 10 carbon atoms, or R ¹ is a furyl group, a thienyl group, a tetrahydrofurfuryl group, an aralkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms, a phenoxy group or a cyano group; R ² represents a group R ¹ or an alkanoyl group having 2 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms, Phenoxycarbonyl group, -N (
R ⁴ ) represents a (R ⁵ ) group, a morpholino group or a piperidino group, or R ¹ and R ² together with the carbon atom to which they are attached are a 5- to 8-membered ring or one benzo group or two and bound 5 to form a 8-membered ring, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkanoyl group or a benzoyl group 6 2 -C, and R ⁵ 4. The method according to claim 3, wherein represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group. (5) In the formula II, n is 1 and R ³ is an alkyl group having 1 to 18 carbon atoms; an unsubstituted or halogen atom, an alkyl group having 1 to 16 carbon atoms, 1 to 4 carbon atoms. A haloalkyl group, an aminoalkyl group having 1 to 4 carbon atoms and 1 carbon atom
C4 -C4 alkoxy, C1 -C4 alkylcarbonyl, C1 -C4 alkylcarbonyloxy, benzoyl, benzoyloxy, hydroxyl, carboxyl, C1 -C4 alkoxy A carbonyl group, an alkyl-CONH- group having 1 to 4 carbon atoms, phenyl-C
ONH- group, H ₂ N-group, an alkyl -NH- group of C 1 -C 4, di (alkyl of 1 to 4 carbon atoms) -N- group or 6 to carbon atoms substituted by a nitro group Represents 10 aryl groups; or R ³ has 5 to 1 carbon atoms
A cycloalkyl group having 2 carbon atoms; an aralkyl group having 7 to 9 carbon atoms; a trifluoromethyl group; or a trichloromethyl group; or n is 2, and R ³ is an alkylene group having 2 to 12 carbon atoms. Represents an arylene group having 6 to 15 carbon atoms or an aralkylene group having 7 to 12 carbon atoms, any of which is unsubstituted or an alkyl group having 1 to 16 carbon atoms, a halogen atom, or a hydroxyl group. any non-interrupted or -O- group of these and which, is substituted by, -S- group or a -NR ⁵ - group (wherein, R ⁵ is a hydrogen atom, an alkyl of 1 to 12 carbon atoms Or a cyclohexyl group). (6) In the formula II, n is 1 and R ³ is an alkyl group having 1 to 12 carbon atoms, or unsubstituted or substituted by a halogen atom, an alkyl group having 1 to 16 carbon atoms or a hydroxyl group. 6. The method according to claim 5, wherein the phenyl group is a phenyl group. (7) In formula II, ^one of R ¹ and R ² represents a phenyl group or a 4-methoxyphenyl group, and the other represents a cyano group, or R ¹ and R ² are those to which they are bonded. R ³ represents a 4-tolyl, 4-chlorophenyl or 4-dodecylphenyl group together with carbon atoms to form a fluorene or anthrone ring system, m is 0 and n is 1 The method of claim 3. (8) The method according to claim 1, wherein the film-forming organic material (A) contains a phenolic hydroxyl group or a carboxylic acid group or a sulfonic acid group. (9) The film-forming organic material (A) is a homopolymer or copolymer of an ethylenically unsaturated phenol polymer, a novolak resin or an ethylenically unsaturated carboxylic acid or carboxylic anhydride. Method. (10) and (A) a film-forming organic material, (B) the following formula I:> C = N-O -SO 2 - at least one of the at least one and aromatic groups of the oxime sulfonate group represented by I Used as a positive photoresist , consisting of a mixture with
The composition used. (11) The indicated carbon atom or sulfur atom in the substance (B) is bonded to a group containing an aromatic ring, or the indicated carbon atom and the indicated sulfur atom each contain an aromatic ring. 11. The composition according to claim 10, wherein said composition is bound to: (12) The substance (B) has the following formula II: Wherein R ¹ represents a monovalent aliphatic, carbocyclic, heterocyclic or araliphatic group having up to 20 carbon atoms, or a cyano group; R ² represents a group R ¹ or unsubstituted or substituted amino R ¹ and R ² together with the carbon atom to which they are attached form a carbocyclic or heterocyclic group having up to 20 carbon atoms, and R ³ represents a carbon atom Represents an n-valent aliphatic, carbocyclic, heterocyclic group having up to 40 or an unsubstituted or substituted amino group, provided that at least one of R ¹ , R ² and R ³ is a carbocyclic aromatic or heterocyclic group; Containing a cyclic aromatic group, m is 0 or 1, and n is 1 or 2. 11. The composition according to claim 10, which is represented by the formula: (13) In the formula II, R ¹ is an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms. , Unsubstituted or the following groups: halogen atom, 1 to 16 carbon atoms
With one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group, a phenylthio group and a nitro group. Represents an aryl group having 6 to 10 carbon atoms, or R ¹ represents a furyl group, a thienyl group, a tetrahydrofurfuryl group, an aralkyl group having 7 to 12 carbon atoms, a 1 to 8 carbon atoms.
Represents an alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, a phenoxy group or a cyano group; R ² represents a group R ¹ or an alkanoyl group, a benzoyl group having 2 to 6 carbon atoms, Alkoxycarbonyl group, phenoxycarbonyl group, -N (
R ⁴ ) represents a (R ⁵ ) group, a morpholino group or a piperidino group, or R ¹ and R ² together with the carbon atom to which they are attached are a 5- to 8-membered ring or one benzo group R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkanoyl group having 2 to 6 carbon atoms or a benzoyl group; 13. The composition according to claim 12, wherein ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group. (14) In the formula II, n is 1 and R ³ is an alkyl group having 1 to 18 carbon atoms; an unsubstituted or halogen atom, an alkyl group having 1 to 16 carbon atoms, 1 to 4 carbon atoms. A haloalkyl group, an aminoalkyl group having 1 to 4 carbon atoms and 1 carbon atom
C4 -C4 alkoxy, C1 -C4 alkylcarbonyl, C1 -C4 alkylcarbonyloxy, benzoyl, benzoyloxy, hydroxyl, carboxyl, C1 -C4 alkoxy A carbonyl group, an alkyl-CONH- group having 1 to 4 carbon atoms, phenyl-C
ONH- group, H ₂ N-group, an alkyl -NH- group of C 1 -C 4, di (alkyl of 1 to 4 carbon atoms) -N- group or 6 to carbon atoms substituted by a nitro group Or R ³ represents a cycloalkyl group having 5 to 12 carbon atoms; an aralkyl group having 7 to 9 carbon atoms; a trifluoromethyl group; or a trichloromethyl group; And R ³ represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 15 carbon atoms or an aralkylene group having 7 to 12 carbon atoms, any of which is unsubstituted Or substituted by an alkyl group having 1 to 16 carbon atoms, a halogen atom, or a hydroxyl group, and any of these is uninterrupted or an -O- group. -S- group or -NR ^5,
- (wherein, R ⁵ is a hydrogen atom, an alkyl group or a cyclohexyl group having 1 to 12 carbon atoms.) Group composition of paragraph 12, wherein claims which is interrupted by. (15) In the formula II, n is 1 and R ³ is an alkyl group having 1 to 12 carbon atoms, or unsubstituted or substituted by a halogen atom, an alkyl group having 1 to 16 carbon atoms or a hydroxyl group. Claim 14 which represents a phenyl group
The composition according to Item. (16) In formula II, ^one of R ¹ and R ² represents a phenyl group or a 4-methoxyphenyl group, and the other represents a cyano group, or R ¹ and R ² are bonded to each other. R ³ represents a 4-tolyl, 4-chlorophenyl or 4-dodecylphenyl group together with carbon atoms to form a fluorene or anthrone ring system, m is 0 and n is 1 13. A composition according to claim 12. (17) The composition according to claim 10, wherein the film-forming organic material (A) contains a phenolic hydroxyl group, a carboxylic acid group or a sulfonic acid group. (18) The film-forming organic material (A) according to claim 17, which is a polymer of an ethylenically unsaturated phenol, a novolak resin, or a homopolymer or copolymer of an ethylenically unsaturated carboxylic acid or carboxylic anhydride. Composition. (19) The composition according to claim 10, wherein (B) is contained in an amount of 0.05 to 0.8 part by weight based on part by weight of (A).